Compositions comprising a thermoplastic component and superabsorbent polymer

ABSTRACT

The present invention relates to a composition comprising a thermoplastic component and at least one superabsorbent polymer, methods of use for such composition, and articles comprising such composition. The composition may be formed into a film layer or applied to an article with various hot melt adhesive application techniques. The composition is useful for a variety of end-uses, particularly for use in disposable absorbent articles such as disposable diapers, feminine napkins and medical dressings.

RELATED APPLICATIONS

This application is a Continuation-In-Part of U.S. patent applicationSer. No. 60/084,582 filed May 7, 1998.

FIELD OF THE INVENTION

The present invention relates to a composition comprising athermoplastic component and at least one superabsorbent polymer, methodsof use for such composition, and articles comprising such composition.The composition may be formed into a film layer or applied to an articlewith various hot melt adhesive application techniques. The compositionis useful for a variety of end-uses, particularly for use in disposableabsorbent articles such as disposable diapers, feminine napkins andmedical dressings.

BACKGROUND OF THE INVENTION

Water-insoluble, water swellable hydrogel-forming absorbent polymers,also referred to as superabsorbent polymers (SAP), are capable ofabsorbing large quantities of liquids such as water, body fluids (e.g.,urine, blood), industrial fluids, household fluids and are furthercapable of retaining such absorbed liquids under moderate pressures.

For example, SAP is employed in various cable applications to shield thepenetration of moisture. When the outer sheath of the cable is damagedallowing penetration of fluids, the SAP absorbs the incoming liquid andswells, forming a physical barrier to the entry of any further fluid.Particulate SAP is typically held in place by means of a hydrosolublebinder. For example, U.S. Pat. No. 4,837,077 issued to Anton et al.,Jun. 6, 1989, relates to a hydroexpansible composite material includinga solid flat support having on at least one of its faces a coating witha high proportion of a hydroexpansible polymer powder fixed to thesupport by means of a hydrosoluble binder, the coating being essentiallyformed of 95% to 55% by weight of a hydroexpansible polymer powder, 5%to 23% by weight of a hydrosoluble binder, and surfactant in a positiveamount of up to 22% by weight. The ingredients are homogenized by meansof a liquid. This reference expressly teaches that thermoplasticsubstances cause an unfavorable effect, the blockage of a part of thehydroexpansible polymer powder, thus limiting its ability to swell inthe presence of water.

The absorption characteristics of SAP materials make them especiallyuseful for incorporation into absorbent articles such as disposablediapers, adult incontinent pads and briefs, and catamenial products suchas sanitary napkins and the like. A desired characteristic of suchdisposable absorbent articles is thinness. Thinner disposable articlesare less bulky to wear, better fitting under clothing and are lessnoticeable. Further, thin disposable absorbent articles are morecompact, making the product easier for the consumer to carry and store.Compactness in packaging also results in reduced distribution costs forthe manufacturer and the distributor, including less shelf space. Theability to provide thinner absorbent articles such as a diaper has beencontingent on the ability to develop relatively thin absorbent cores orstructures that can acquire and store large quantities of fluid,particularly urine. Therefore, there is a trend towards employing higherconcentrations of SAP polymers to achieve this purpose.

SAP is typically available in a particulate or powder form that issprinkled or sifted into the absorbent core portion, which is sandwichedbetween a fluid pervious topsheet and a fluid impervious backsheet. Theincorporation of particulate SAP into an article tends to generate dustfrom the SAP fines. Further, conventional absorbent articles have thelimitation that the absorbent gelling particles are not immobilized andare free to migrate and shift during the manufacturing process and/oruse. Movement of the SAP particles during manufacture can lead toabsorbent material handling losses during manufacturing operations aswell as improper distribution of the particles.

Other problems occur when these absorbent gelling particles migrateduring and after swelling. The inability to fix the particles at optimumlocations leads to insufficient fluid storage in one area andover-capacity in other areas due to the movement of the SAP particles tolocations other than where originally positioned. Another importantfactor that has to be considered is the liquid permeability of the SAP.It has been discovered that the fluid transport properties of the gellayer formed as a result of the swelling SAP particles in the presenceof fluids is extremely important. Although the formation of a SAP gellayer fluid barrier, known as “gel blocking” is desirable for someapplications, such as for use in cables, the formation of gel layers indisposable absorbent products is undesirable since it greatly reducesthe efficiency of the SAP. Thus, the advantages of being able to fixateSAP in place are apparent and several ways of accomplishing such havebeen suggested.

For example, U.S. Pat. No. 4,392,908 issued to Dehnel Jul. 12, 1983,concerns a process for manufacturing a water-absorbent article in whichparticles of a water swellable polymer are fixed to a water-absorbentsubstrate. The process includes the steps of forming on the surface ofwater-swellable particles a coating of a thermoplastic adhesive resin;locating the coated particles in their unswollen state and dry state onor within the water-absorbent substrate also in the dry state; andapplying heat to soften the thermoplastic coating of the particles andpressing the particles and substrate to cause the particles to be boundto the substrate. The particles of absorbent material can be coated bymixing the absorbent particle with an aqueous latex of the resin andthen drying the mixture, spraying a resin solution or latex onto theparticles, adding the resin to the particles when the particles are in aslurry, or incorporating the thermoplastic as a solution or latex duringthe manufacture of the absorbent material.

Further, SAP particles may be combined with certain thermoplasticcompositions.

U.S. Pat. No. 4,977,211 issued to Doi, Dec. 11, 1990, teaches a moldablewater-absorptive resin composition which comprises (A) 5% to 95% byweight of a water-absorptive resin and 95% to 5% by weight of (B) apolyolefin resin and (C) an ethylene/alpha-olefin copolymer rubber basedon the total content of said components (A), (B) and (C), wherein thecontents of (C) amounts to 20% to 80% by weight based on the totalcontents of said component (B) and (C). An ethylene/vinyl acetatecopolymer is exemplified having a vinyl acetate content of 33% by weightand a melt index of 30 g/10 min. Subsequently, the water-absorptiveresin composition of the present invention can be molded into a formsuitable for its final use. The molded products may be subjected to asecondary molding treatment such as foaming or orientation. Thecompositions can be molded alone into a film, a sheet, fibers or otherproducts.

Japanese Patent Application 9-176618 published Jul. 8, 1997 relates to awater-swelling hot melt presealant for lap joint construction externalwall material. The composition includes 20 wt-% to 50 wt-% thermoplasticelastomer, 5 wt-% to 40 wt-% tackifier, 10 wt-% to 50 wt-% plasticizerand 5 wt-% to 35 wt-% water swellable resin. The plasticizer isdescribed as paraffin type oil, naphthene type oil, aromatic type oil,polybutene liquid rubber, polyisobutylene liquid rubber, polyisopreneliquid rubber and its hydrogenated product.

Japanese Patent Application 60-195299, published Oct. 3, 1985 pertainsto a method for preventing water leaks with good operability, especiallyin engineering work and construction employing a water-swellablecomposition styrene elastomers, highly water absorbing materials andtackifiers. The proportions of the ingredients are usually 5-100 partsof the highly water-absorbing resin and 100 to 200 parts of tackifierbased on 100 parts of the styrene elastomer.

More recently, WO 98/27559A1, published Jun. 25, 1998 concerns a waterswellable thermoplastic compound for gluing and coating made from awater insoluble component, a water soluble or water dispersiblecomponent, and a water-swellable component. Examples of suitablewater-soluble or water dispersible oligomers, homopolymer or copolymersinclude polyethylene glycol in the molecular weight range between 2400and 20,000, polyvinyl methyl ether, polyvinylpyrrolidone, copolymers ofvinyl methyl ether or vinyl pyrrolidone, polyvinyl alcohols, watersoluble or water dispersible polyesters or copolyesters, and watersoluble or water dispersible acrylate polymers.

SUMMARY OF THE INVENTION

The present inventors have discovered that the inclusion of watersoluble or dispersible polymers disadvantageously reduces the rate offluid acquisition. It is surmised that water soluble/dispersiblepolymers compete with the SAP in absorption of the fluid. In suchinstances, the water soluble or dispersible ingredient forms a solutionor dispersion that thickens the fluid intended to be absorbed by theSAP. The thickened fluid tends to be absorbed by the SAP at a muchslower rater than that of the fluid prior to thickening, thus hinderingthe rate of absorption.

Surprisingly, the present applicants have found that the fluidacquisition rate and the total absorption capacity for small particlesize SAP is not impaired by being admixed with certain thermoplasticcompositions. Further, in many instances the presence of thethermoplastic component actually enhances the performance of the SAP,particularly for reducing unintended gel blocking.

The present invention is a composition comprising a thermoplasticcomposition, also referred to as the “thermoplastic component” and atleast one superabsorbent polymer. The thermoplastic component issufficiently polar and simultaneously of relatively low cohesivestrength. The cohesive strength corresponds to the melt index of apolymer or molten viscosity of a mixture of a thermoplastic polymer andother ingredients.

In one embodiment, the present invention is a thermoplastic compositioncomprising a thermoplastic component comprising at least onethermoplastic polymer and at least one water insoluble diluent havingpolar functionality and at least one superabsorbent polymer. Thethermoplastic component is preferably water insoluble. The diluent ispreferably a plasticizer employed at a concentration ranging from about10 wt-% to about 30 wt-% of the total weight of the composition.

In another embodiment, the present invention is a thermoplasticcomposition comprising a thermoplastic component comprising at least oneinterpolymer of ethylene. The interpolymer has a melt index greater thanabout 500 g/10 min., preferably about 800 g/10 min. and greater, andmore preferably about 1000 g/10 min. and greater. Further, theinterpolymer of ethylene preferably has a comonomer content of greaterthan 25 wt-% and preferably greater than about 28 wt-% or higher. Thecomonomer is preferably vinyl acetate, methacrylate, n-butyl acrylateand mixtures thereof. Further, the composition is preferably free ofwater soluble/dispersible polymers having a molecular weight (Mw) ofgreater than 2000.

In another embodiment, the present invention is a thermoplasticcomposition comprising about 25 wt-% to about 50 wt-% of a thermoplasticcomponent having a viscosity of less than about 30,000 cPs at 177° C.and 50 wt-% to about 75 wt-% of a superabsorbent polymer.

The thermoplastic component may be a single thermoplastic polymer or ablend of thermoplastic polymers in its entirety. Alternatively, thethermoplastic component may comprise at least one thermoplastic polymerin combination with at least one hot melt adhesive ingredient such asplasticizers, tackifiers and waxes. The thermoplastic component ispreferably present in an amount ranging from about 40 wt-% to about 70wt-%, whereas the superabsorbent polymer is preferably present in anamount ranging from about 30 wt-% to about 60 wt-%. Further, thethermoplastic component preferably comprises at least one thermoplasticpolymer including block copolymers, amorphous polyolefins, crystallinepolyolefins, interpolymers of ethylene and mixtures thereof.

The composition preferably gels at a rate equal to or faster than thatof the SAP polymer alone, particularly when employing SAP having aparticle size of less than about 200 microns. The rate of gelation ispreferably less than 3 hours, more preferably less than 1 hour and mostpreferably less than about 30 minutes.

The resulting composition can be used in place of particulate orpowdered SAP for any application employing such, avoiding theaforementioned problems. The composition can advantageously be appliedto an article by any known hot melt application technique, extruded as arod, strand or fiber, as well as be formed into a film layer on asubstrate, thus providing SAP in a roll good form.

In another embodiment, the invention is film layer disposed on asubstrate comprising the inventive thermoplastic mixture. The film layermay be formed by providing a molten mixture of the inventive compositioncomprising at least one thermoplastic polymer and at least onesuperabsorbent polymer and forming a substantially continuous film fromsaid molten mixture onto a substrate.

In another embodiment, the invention is a method of applyingsuperabsorbent polymer to a substrate comprising the steps of:

a) providing a molten mixture comprising a thermoplastic composition andat least one superabsorbent polymer; and

b) applying said mixture to a substrate.

DETAILED DESCRIPTION OF THE INVENTION

The term “thermoplastic composition” and “thermoplastic component”refers to a composition that is reversibly capable of softening orfusing when heated and hardening again when cooled.

The term “molten” as used herein refers to a flowable or liquified stateof matter attained with heat.

The terms “water responsive” and “water sensitive” as used herein refersto ingredients that are soluble or dispersible in an aqueousenvironment. Aqueous environment includes neutral, basic, acidic andionic aqueous solutions.

The term “water insensitive” as used herein refers to an ingredient thatis soluble in water at a concentration less than 1.0 wt-%, andpreferably less than 0.5 wt-%.

The present invention is a composition comprising a thermoplasticcomposition and at least one super absorbent polymer (SAP). Thethermoplastic component provides the thermoplasticity of the SAPcontaining composition, whereas the SAP polymer provides the fluidabsorption capability of the composition. The thermoplasticity allowsfor a variety of application techniques, such as those employed for hotmelt adhesives. The thermoplastic component also solves the gel blockingproblem. Gel blocking is the phenomena wherein SAP particles absorbfluid and swell into a gel layer. The gel layer creates a barrier andprevents the migration of fluid to the ungelled SAP particles. Since thethermoplastic component provides a means of separating the individualsmall particle size SAP particles from each other, each SAP particle canabsorb fluid and swell independently, essentially unaffected byneighboring SAP particles. Hence gel blocking is reduced, increasing therate of absorption of the SAP.

The thermoplastic component is sufficiently polar and simultaneously ofrelatively low cohesive strength. Both these properties are contributedto by the selection of ingredients employed. The thermoplastic componentcomprises at least one thermoplastic polymer and at least one waterinsoluble diluent having polar functionality or at least oneinterpolymer of ethylene having a melt index greater than about 500 g/10min and a comonomer content greater than about 25 wt-%, or athermoplastic composition having a viscosity of less than about 30,000cPs at 350° F. (177° C.) in combination with at least 50 wt-%superabsorbent polymer. The thermoplastic component is present at aconcentration sufficient to form a continuous phase within the mixture.Hence, the concentration of thermoplastic component is dependent on theconcentration and particle size of the superabsorbent polymer employed.In general, the thermoplastic component comprises from about 20 wt-% toabout 80 wt-%, preferably from about 30 wt-% to about 70 wt-%, and mostpreferably from about 40 wt-% to about 60 wt-%.

The thermoplastic composition may comprise, in its entirety, a singlethermoplastic polymer, a blend of thermoplastic polymers, oralternatively the thermoplastic composition may be a hot melt adhesivecomprising at least one thermoplastic polymer in combination with otherthermoplastic diluents such as tackifying resins and plasticizers. Theinvention also contemplates the thermoplastic composition beingcomprised entirely of at least one thermoplastic tackifier, plasticizer,wax and mixtures thereof. However, in most instances, a thermoplasticpolymer is necessary to provide the desired properties, particularlystrength. The thermoplastic polymer alone may exhibit sufficientadhesive characteristics for some applications. However, preferably thethermoplastic polymer is combined with tackifiers and plasticizers tomodify the adhesive properties for use in the intended application. Thisembodiment is particularly useful wherein the composition serves a dualpurpose of providing the SAP in a non-particulate form as well asfixating the SAP in place. SAP containing hot melt adhesive may alsoserve the function of bonding at least one substrate layer to at leastone other substrate layer.

The thermoplastic component of the present invention typically comprisesat least one thermoplastic polymer present in an amount ranging fromabout 10 wt-% to about 60 wt-%, preferably in an amount ranging fromabout 15 wt-% to about 50 wt-%, and more preferably in an amount rangingfrom about 20 wt-% to about 50 wt-%, with respect to the total weight ofthe composition.

For embodiments that employ only a single thermoplastic polymer as theentire thermoplastic component, the thermoplastic polymer will typicallyeither be sufficiently polar and/or combined with a polar diluent. Inthe case of employing blends of thermoplastic polymers as the entirethermoplastic component, the blend will exhibit the same desiredproperties. For some embodiments, a relatively high viscositythermoplastic polymer is combined with relatively low viscositythermoplastic components to enhance the cohesive strength of the mixturewhile maintaining good processability. For this embodiment, therelatively high viscosity polymer generally has a melt index (MI) ofabout 400 g/10 min. or less preferably about 200 g/10 min. or less, morepreferably about 100 g/10 min. or less and most preferably less thanabout 50 g/10 min. In order to achieve the desired polarity or moltenviscosity profile, these relatively high viscosity polymers may only beemployed at minimal concentrations, typically in an amount less thanabout 40 wt-%, preferably from about 5 wt-% to about 30 wt-%, and morepreferably from about 10 wt-% to about 25 wt-%, with respect to thetotal weight of the composition.

Accordingly, a wide variety of thermoplastic polymers are suitable foruse in the present invention. Such thermoplastic polymers are preferablywater insensitive. Exemplary polymers for use in the invention includestyrenic block copolymers, amorphous and crystalline polyolefinsincluding homogeneous and substantially linear ethylene/alpha-olefininterpolymers; interpolymers of ethylene such as ethylene-vinyl-acetate(EVA), ethylene-methyl acrylate (EMA) and ethylene n-butyl acrylate(EnBa); and mixtures thereof.

A wide variety of block copolymers are useful in the present inventionincluding A-B-A triblock structures, A-B diblock structures, (A-B)_(n)radial block copolymer structures, as well as branched and graftedversions of such, wherein the A blocks are non elastomeric polymerblocks, typically comprising polystyrene, and the B blocks areunsaturated conjugated diene or hydrogenated version thereof. Ingeneral, the B block is typically isoprene, butadiene, ethyleneibutylene(hydrogenated butadiene), ethylene/propylene (hydrogenated isoprene),and mixtures thereof. Commercial embodiments include the Kratont® D andG series block copolymers, available from Shell Chemical Company(Houston, Tex.), Europrenet® Sol T block copolymers available fromEniChem (Houston, Tex.), Vector® block copolymers available from Exxon(Dexco) (Houston, Tex.), as well as others. Block copolymer basedcompositions are particularly useful for pressure sensitive adhesiveapplications which generally employ a relatively low melt index blockcopolymer (less than 50 g/10 min) in combination with at least onetackifying resin and plasticizing oil.

Amorphous polyolefins or amorphous polyalphaolefms (APAO) arehomopolymers, copolymers, and terpolymers of C₂-C₈ alphaolefins. Thesematerials are typically polymerized by means of processes which employZiegler-Natta catalysts resulting in a relatively broad molecular weightdistribution. Commercially available amorphous polyalphaolefins includeRextac® and REXFlex® propylene based homopolymers, ethylene-propylenecopolymers and butene-propylene copolymers available from Rexene(Dallas, Tex.) as well as Vestoplast® alpha-olefin copolymers availablefrom Hils (Piscataway, N.J.).

Metallocene polyolefins are homogeneous linear and substantially linearethylene polymers prepared using single-site or metallocene catalysts.Homogeneous ethylene polymers are characterized as having a narrowmolecular weight distribution and a uniform short-chain branchingdistribution. In the case of substantially linear ethylene polymers,such homogeneous ethylene polymers are further characterized as havinglong chain branching. Substantially linear ethylene polymers arecommercially available from The Dow Chemical Company as Affinity™polyolefin plastomers, which are produced using Dow's Insite™technology, whereas homogeneous linear ethylene polymers are availablefrom Exxon Chemical Company under the tradename Exact®g. Homogeneouslinear and substantially linear ethylene polymers having a relativelylow density, ranging from about 0.855 to about 0.885, and a relativelylow melt index, for example less than about 50 g/10 min. are mostpreferred, particularly for creating elastomeric fibers, films andadhesive compositions that swell upon exposure to water.

The term “interpolymer” is used herein to indicate a copolymer,terpolymer, or higher order polymer. That is, at least one othercomonomer is polymerized with ethylene to make the interpolymer.Interpolymers of ethylene are those polymers having at least onecomonomer selected from the group consisting of vinyl esters of asaturated carboxylic acid wherein the acid moiety has up to 4 carbonatoms, unsaturated mono- or dicarboxylic acids of 3 to 5 carbon atoms, asalt of the unsaturated acid, esters of the unsaturated acid derivedfrom an alcohol having 1 to 8 carbon atoms, and mixtures thereof.

If employed uncompounded, the ethylene to unsaturated carboxyliccomonomer weight ratio is preferably greater than about 3:1, morepreferably about 2:1. Hence the comonomer concentration is preferablygreater than 30 wt-%, more preferably greater than 33 wt-% and mostpreferably greater than 35 wt-%, with respect to the total weight of theethylene interpolymer. The melt index of the interpolymers of ethylenemay range from about 50 to about 2000, preferably from about 100 to1500, more preferably from about 200 to 1200, and most preferably fromabout 400 to 1200 g/10 min. When employing a polymer having too low of amelt index uncompounded, the strength of the polymer tends to constrainthe swelling of the SAP particles. However, as previously discussed, thedisadvantages of the lower melt index interpolymers of ethylene can beovercome by formulating the polymer with diluents.

Suitable ethylene/unsaturated carboxylic acid, salt and esterinterpolymers include ethylene/vinyl acetate (EVA) ethylene/acrylic acid(EEA) and its ionomers; ethylene/methacrylic acid and its ionomers;ethylene/methyl acrylate (EMA); ethylene/ethyl acrylate;ethylene/n-butyl acrylate (EnBA); as well as various derivatives thereofthat incorporate two or more comonomers.

Other suitable thermoplastic polymers that may be employed includepolylactide, caprolactone polymers, and poly(hydroxy-butyrate/hydroxyvalerate), certain polyvinyl alcohols,biodegradable copolyesters such as Eastman Copolyester 14766 (Eastman),linear saturated polyesters such as Dynapol or Dynacoll polymers fromHüils, poly(ethylene oxide)polyether amide and polyester ether blockcopolymers available from Atochem (PeBax) or Hoechst Celanese(Rite-flex) respectively, and polyamide polymers such as those availablefrom Union Camp (Unirez) or Huls (Vestamelt) or EMS-Chemie (Griltex).

Alternatively, water soluble or water dispersible polymer may beemployed provided such polymers are combined with water insoluble polaringredients such as tackifiers, plasticizers and waxes such that thewater sensitivity of the thermoplastic component as a whole issufficiently reduced such that the composition exhibits the desired rateof acquisition. Representative water soluble or water dispersiblepolymers that may be employed in this manner include water solublepolyamides such as those described in U.S. Pat. No. 3,882,090,incorporated herein by reference, amorphous water sensitivethermoplastic polymers such as polyvinyl alcohol (PVOH) available fromNippon Grohsei as Grohseran L-301 and Grohseran L-302, polyvinylpyrrolidone (PVP) available from BASF and ISP, polyvinylpyrrolidone/vinyl acetate copolymer (PVPNVA) available from ISP,polyetheroxazoline available from Dow under the tradename PEOX and fromPCI Incorporated under the tradename Aquazol, polyvinyl methyl etheravailable from Amoco Chemical Co. under the tradename Amobond, linearpolyesters, polyvinyl alcohol, polyacrylamide, water dispersiblecopolyesters (Eastman AQ).

The thermoplastic component of the composition of the present inventionpreferably further comprises at least one additional ingredient in anamount up to about 50 wt-%, and preferably from about 10 wt-% to about40 wt-% with respect to the total composition. Preferred thermoplasticingredients include those that are commonly employed in hot meltadhesive compositions including plasticizers, tackifiers, waxes, andadditives such as antioxidants and pigments. In general, the type ofthermoplastic ingredient(s) will be selected to insure sufficientcompatibility of the thermoplastic component as a whole. In a preferredembodiment, the thermoplastic component of the composition of thepresent invention comprises at least one diluent having polarfunctionality. The diluent is preferably a plasticizer or wax having amolecular weight (Mw) of less than 3000 and preferably less than 2000.The diluent is preferably water insensitive, yet sufficiently polar toreduce the surface tension and/or contact angle of the thermoplasticcomposition relative to a comparative composition comprising the sameingredients in the absence of such ingredient. Polar diluents includeplasticizers and waxes having at least one polar group per molecule. Thepolar group may be a terminal group or bonded to one or more units inthe middle of the molecule. Polar groups include alcohol, ether, ester,epoxy, carboxylic acid, amine, amide, aldehyde, keton, oxime, sulphonicacid, and sulfonamide groups. It is surmised that the polar diluent mayplasticize the SAP. Hence, combining the SAP with polar plasticizeralone may increase the absorption rate. However, in the absence of apolymer, plasticizer alone typically could not contribute a continuousthermoplastic phase to disperse the SAP within. Preferably, the diluentis employed at an amount ranging from about 5 wt-% to about 30-wt-% andmore preferably in an amount ranging from about 10 wt-% to about 20 wt-%of the total composition.

Exemplary polar plasticizers include phthalate plasticizers such asdioctyl phthalate and butyl benzyl phthalate (e.g., Santicizer 160 fromMonsanto); liquid polyesters such as Dynacol 720 from Huls and liquidpolymeric plasticizer available from C. P. Hall; benzoate plasticizerssuch as 1,4-cyclohexane dimethanol dibenzoate (e.g., Benzoflez 352 fromVelsicol), diethylene glycol/dipropylene glycol dibenzoate (e.g.,Benzoflez 50 from Velsicol), and diethylene glycol dibenzoate where themole fraction of hydroxyl groups which have been esterified ranges from0.5 to 0.95 (e.g., Benzoflex 2-45 High Hydroxyl also from Velsicol);phosphite plasticizers such as t-butyl diphenyl phosphate (e.g.,Santicizer 154 from Monsanto); liquid rosin derivatives having Ring andBall softening points below about 60° C. such as methyl ester ofhydrogenated rosin (e.g., Hercoyn D from Hercules); as well as vegetableand animal oils such as glycerol esters of fatty acids and polymerizableproducts thereof. Preferred plasticizers include esters of citric acidsuch as Citroflex® 2, A-2, 4, A-4, A-6, and B-6; butyl benzyl phthalate,toluene sulfonamide, benzoate plasticizers such as 1,4-cyclohexanedimethanol dibenzoate, diethylene glycol/dipropylene glycol dibenzoate,and diethylene glycol dibenzoate where the mole fraction of hydroxylgroups which have been esterified ranges from 0.5 to 0.95.

Further, water soluble or water dispersible plasticizers may also beemployed, provided the presence thereof does not impede the rate ofabsorption of the SAP. Suitable examples include polyethylene glycolwith molecular weight below about 2000 and preferably less than 1000,derivatives of polyethylene glycol including Pycal 94, the phenyl etherof PEG available from ICI; ethoxylated bis phenol A (e.g., Macol 206 EMfrom PPG Industries) and dionyl phenol ethyloxylates (e.g., Surfonic DNPfrom Huntsman Chemical Corp.).

Exemplary polar waxes include 12-hydroxystearamide, N-(2-hydroxy ethyl12-hydroxy stearamide (Paricin 220 and 285 from CasChem), stearamide(Kemamide S from Witco), glycerin monostearate, sorbitan monostearate,and 12-hydroxy stearic acid. Also useful in combination with the aboveare less polar waxes such as N,N′-ethylene-bis stearamide (Kemamide W-40from Witco), hydrogenated castor oil (castor wax), oxidized syntheticwaxes, and functionalized waxes such as oxidized polyethylene waxes(Petrolite E-1040).

Other useful plasticizers that may be employed include hydrocarbon oils,polybutene, liquid tackifying resins and liquid elastomers. Plasticizeroils are primarily hydrocarbon oils which are low in aromatic contentand which are paraffinic or naphthenic in character. Plasticizer oilsare preferably low in volatility, transparent and have as little colorand odor as possible. The use of plasticizers in this invention alsocontemplates the use of olefin oligomers, low molecular weight polymers,vegetable oils and their derivatives and similar plasticizing liquids.

Waxes are usefully employed to reduce viscosity as well as increase theblocking resistance at concentrations ranging from about 2 wt-% to about25 wt-% and preferably from about 10 wt-% to about 20 wt-%. Largerconcentrations of waxes are typically avoided since waxes tend to bloomto the surface during cooling of the thermoplastic component creating afluid impermeable barrier layer at the surface of the composition orencapsulating the SAP, thus hindering the ability of the SAP to absorbfluid. In addition to the preferred polar waxes, other useful waxesinclude paraffin waxes, microcrystalline waxes, Fischer-Tropsch,polyethylene and by-products of polyethylene.

As used herein, the term “tackifier” means any of the compositionsdescribed below that are useful to impart tack to the hot melt adhesivecomposition. ASTM D-1878-61T defines tack as “the property of a materialwhich enables it to form a bond of measurable strength immediately oncontact with another surface”.

The composition of the invention may comprise up to about 50 wt-% of atackifying resin. Tackifying resins are preferably employed at aconcentration ranging from about 5 wt-% to about 40 wt-% and morepreferably from about 10 wt-% to about 20 wt-% with respect to the totalweight of the composition.

Tackifying resins comprise resins derived from renewable resources suchas rosin derivatives including wood rosin, tall oil and gum rosin aswell as rosin esters, natural and synthetic terpenes and derivatives ofsuch. Aliphatic, aromatic or mixed aliphatic-aromatic petroleum basedtackifiers are also useful in the invention. Representative examples ofuseful hydrocarbon resins include alpha-methyl styrene resins, branchedand unbranched C₅ resins, Cg resins and C₁₀ resins, as well as styrenicand hydrogenated modifications of such. Tackifying resins range frombeing a liquid at 37° C. to having a ring and ball softening point ofabout 135° C.

As is known in the art, various other components can be added to modifythe tack, color, odor, etc., of the thermoplastic composition. Additivesincluding antioxidants such as hindered phenolics (e.g., Irganox™ 1010,Irganox™ 1076), phosphites (e.g., Irgafos™ 168), antiblock additives,pigments and fillers, can also be included in the formulations.

Hydrophilic fillers are a preferred class of additives, which are usefulto alter the surface properties and/or increase the rate of absorption.Hydrophilic fillers include calcium carbonate, hydroxyethyl cellulose,hydroxypropyl cellulose and starch or cellulose esters, particularly theacetates.

Surfactants are another preferred additive that reduces the surfacetension and/or contact angle of the thermoplastic component. Surfactantsare useful in amounts ranging from about 0.5 wt-% to about 25 wt-% andpreferably from about 5 wt-% to about 15 wt-% with respect to the totalweight of the thermoplastic component. Suitable surfactants includenonionic, anionic, and silicone surfactants. Exemplary nonionicsurfactants are: Ethoxylates of (i) C sub 1-C sub 18, preferred C sub8-C sub 9 alkyl or dialkyl phenols, such as those sold under thetradenames Macol DNP-10, available from PPG Industries, Gurnee, Ill., a10 mole ethoxylate of dinonyl phenol, and Triton X-100, available fromUnion Carbide, a 10 mole ethoxylate of octyl phenol; (ii) alkyl C sub8-C sub 60 mono-alcohols such as those sold under the tradenamesSurfonic L-12-8, an 8 mole ethoxylate of dodecanol, available fromHuntsman Chemical Co., and Unithox 480, a 38 mole ethoxylate crystallinesurfactant available from Petrolite Specialty Polymers Group, Tulsa,Okla.; and (iii) propylene oxide polymers, such as those sold under thetradename Pluronic, which are ethylene oxide/propylene oxide blockcopolymers having a Mn of 200 to 3000, available from BASF; andbenzoates formed by partial condensation of benzoic acid withhydrophilic di or mono-ols having less than 1000 Mn, such as the productof condensing about three equivalents of benzoic acid with fourequivalent of diethylene glycol, commercially available as XP 1010 fromVelsicol Chemical. A preferred nonionic surfactant blend is Atmer 685,available from ICI Surfactants (Wilmington, Del.).

Suitable anionic surfactants are: C sub 8-C sub 60 alkyl ethoxylatesulfonates, (CH sub 3—(CH sub 2) sub 11-14—(O—CH sub 2 CH sub 2) sub3—SO sub 3-Na sup+, such as, Avenel S30, available from PPG Industries;alkyl C sub 8-C sub 60 sulfonates, such as, Rhodapon UB (C sub 12 —SOsub 3 sup −Na sup+) available from Rhone Poulenc; and alkyl/aromaticsulfonates, such as those sold under the tradename Calsoft.

Suitable silicone surfactants are ethoxylates or propoxylates ofpolydimethyl siloxane, having a number average molecular weight of 500to 10,000, preferably 600 to 6000, such as are sold under the tradenamesSilwet L-77, L-7605, and L-7500 available from OSi Specialties, Danbury,Conn.; and product 193 from Dow Corning.

The preferred surfactants are those with lower molecular weights becausethese have increased compatibility in the adhesive formulations. Themaximum acceptable molecular weight depends on the type of surfactantand the other ingredients in the adhesive formulation.

The thermoplastic component is characterized as having a Brookfieldmolten viscosity of less than about 30,000 cPs at 177° C., preferablyless than about 20,000 cPs, more preferably less than about 10,000 cPs,and even more preferably less than about 5,000 cPs. This viscosityconstraint does not necessarily have a lower limit. However, themajority of thermoplastic compositions contemplated for use generallyhave a viscosity of at least about 50 cPs at 100° C., typically at leastabout 100 cPs, and preferably at least about 200 cPs. The viscosity isnot only critical to the application techniques intended for suchcomposition, but is also critical to the efficiency of the SAP. Thepresent applicants have surprisingly discovered that relatively lowviscosity thermoplastic compositions constrain the swelling of the SAPparticle to a much lesser extent and hence improve the absorption of theSAP with respect to a high viscosity based composition.

The thermoplastic composition of the present invention comprises atleast one SAP polymer admixed with the thermoplastic component. Thesuperabsorbent polymer is present in the composition in an amountranging from about 5 wt-% to about 70 wt-%, preferably from about 35wt-% to about 60 wt-%, more preferably ranging from about 40 wt-% toabout 60 wt-%, and most preferably from about 50 wt-% to about 60 wt-%.The Applicants have found that by employing SAP at concentration greaterthan 30 wt-%, particularly in combination with small particle size SAP,a matrix of SAP is formed with the thermoplastic component. Theapplicants surmise that the formation of this SAP matrix is essential tothe absorption rate of the SAP being unaffected by the presence of thethermoplastic component.

Superabsorbent polymers (SAP), also referred to as water-insolubleabsorbent hydrogel-forming polymers (WAHPs) “hydrogel-forming” polymers,and “hydrocolloids” are known and include polysaccharides such ascarboxymethyl starch, carboxymethyl cellulose, and hydroxypropylcellulose; nonionic types such as polyvinyl alcohol, and polyvinylethers; cationic types such as polyvinyl pyridine, polyvinylmorpholinione, and N,N-dimethylaminoethyl or N,N-diethylaminopropylacrylates and methacrylates, and the respective quaternary saltsthereof. Typically, WABPs useful in the present invention have aplurality of anionic, functional groups, such as sulfonic acid, and moretypically carboxy, groups. Examples of polymers suitable for use hereininclude those which are prepared from polymerizable, unsaturated,acid-containing monomers. Such monomers include the olefinicallyunsaturated acids and anhydrides that contain at least one carbon tocarbon olefinic double bond. More specifically, these monomers can beselected from olefinically unsaturated carboxylic acids and acidanhydrides, olefinically unsaturated sulfonic acids and mixturesthereof.

Some non-acid monomers can also be included, preferably in minoramounts, in preparing the SAPs herein. Such non-acid monomers caninclude, for example, the water-soluble or water-dispersible esters ofthe acid-containing monomers, as well as monomers that contain nocarboxylic or sulfonic acid groups at all. Optional non-acid monomerscan thus include monomers containing the following types of functionalgroups: carboxylic acid or sulfonic acid esters, hydroxyl groups,amide-groups, amino groups, nitrile groups, quaternary ammonium saltgroups and aryl groups (e.g., phenyl groups, such as those derived fromstyrene monomer). These non-acid monomers are well-known materials andare described in greater detail, for example, in U.S. Pat. No. 4,076,663(Masuda et. al), issued Feb. 28, 1978, and in U.S. Pat. No. 4,062,817(Westerman), issued Dec. 13, 1977.

Olefinically unsaturated carboxylic acid and carboxylic acid anhydridemonomers include the acrylic acids typified by acrylic acid itself,methacrylic acid, ethacrylic acid, -chloroacrylic acid, -cyanoacrylicacid, -methylacrylic acid (crotonic acid), -phenylacrylic acid,-acrytoxypropionic acid, sorbic acid, -chlorosorbic acid, angelic acid,cinnamic acid, p-chlorocinnamic acid, -stearylacrylic acid, itaconicacid, citraconic acid, mesaconic acid, glutaconic acid, aconitic acid,maleic acid, fumaric acid, tricarboxyethylene and maleic acid anhydride.

Olefinically unsaturated sulfonic acid monomers include aliphatic oraromatic vinyl sulfonic acids such as vinylsulfonic acid, allyl sulfonicacid, vinyl toluene sulfonic acid and styrene sulfonic acid; acrylic andmethacrylic sulfonic acid such as sulfoethyl acrylate, sulfoethylmethacrylate, sulfopropyl acrylate, sulfopropyl methacrylate, 2-hydroxy3-methacryloxypropyl sulfonic acid and 2-acrylamide-2-methylpropanesulfonic acid.

Other SAPs for use in the present invention contain carboxy groups.These polymers include hydrolyzed starch-acrylonitrile graft copolymers,partially neutralized hydrolyzed starch-acrylonitrile graft copolymers,starch-acrylic acid graft copolymers, partially neutralizedstarch-acrylic acid graft copolymers, saponified vinyl acetate-acrylicester copolymers, hydrolyzed acrylonitrile or acrylamide copolymers,slightly network crosslinked polymers of any of the foregoingcopolymers, partially neutralized polyacrylic acid, and slightly networkcrosslinked polymers of partially neutralized polyacrylic acid. Thesepolymers can be used either solely or in the form of a mixture of two ormore different polymers. Examples of these polymer materials aredisclosed in U.S. Pat. No. 4,076,663 (Masuda et. al), issued Feb. 28,1978, U.S. Pat. No. 4,093,776 (Aoki et. al), issued Jun. 6, 1978, U.S.Pat. No. 4,666,983(Tsubakimoto et. al), issued May 19, 1987, and U.S.Pat. No. 4,734,478 (Tsubakimoto et. al), issued Mar. 29, 1988.

Polymer materials used in making the SAPs are slightly networkcrosslinked polymers of partially neutralized polyacrylic acids andstarch derivatives thereof. More preferably still, the SAPs comprisefrom about 50% to about 95%, more preferably about 75%, neutralized,slightly network crosslinked, polyacrylic acid (i.e., poly (sodiumacrylate/acrylic acid)). Network crosslinking renders the polymersubstantially water-insoluble and, in part, determines the absorptivecapacity and extractable polymer content characteristics of the SAPs.Processes for network crosslinking these polymers and typical networkcrosslinking agents are described in greater detail in U.S. Pat. No.4,076,663 (Masuda et. al), issued Feb. 28, 1978.

While the SAP is preferably of one type (i.e., homogeneous), mixtures ofpolymers can also be used in the present invention. For example,mixtures of starch-acrylic acid graft copolymers and slightly networkcrosslinked polymers of partially neutralized polyacrylic acid can beused in the present invention.

The absorbent gelling particles used in the present invention can have asize, shape and/or morphology varying over a wide range. The absorbentgelling particles may have a large ratio of greatest dimension tosmallest dimension (e.g., granules, flakes, pulveruients, interparticleaggregates, interparticle crosslinked aggregates, and the like) and canbe in the form of fibers, foams and the like.

Particle size is defined as the dimension determined by sieve sizeanalysis. Thus, for example, a particle that is retained on a U.S.A.Standard Testing Sieve with 710 micron openings (e.g., No. 25 U.S.Series Alternate Sieve Designation) is considered to have a size greaterthan 710 microns; a particle that passes through a sieve with 710 micronopenings and is retained on a sieve with 500 micron openings (e.g., No.35 U.S. Series Aftemate Sieve Designation) is considered to have aparticle size between 500 and 710 microns; and a particle that passesthrough a sieve with 500 micron openings is considered to have a sizeless than 500.

For particles of SAPs employed in the present invention, the particlesize ranges from about 10 to about 1000 microns. Smaller particle sizes,particularly at concentrations greater than 30 wt-%, and preferablyabout 40 wt-%, have been found to be particularly useful for creating aSAP matrix within the thermoplastic component. Minimal particle size isalso advantageous to obtain homogeneous mixing as well as reduce theabrasion and nozzle clogging problems associated with processingrelatively large particles using hot melt adhesive applicationequipment. For these reasons the particle size of the SAP is preferablyless than about 500 microns, more preferably less than about 300microns, and more preferably less than about 200 microns. However,larger particle size may also be employed particularly in applicationsin which the SAP particle is equal to or larger than the thickness ofthe thermoplastic component or when an extruder is employed to mixand/or apply the composition.

The composition of the present invention is preferably made by firstpreparing the thermoplastic component by melting and blending all thethermoplastic ingredients and then adding the SAP to the moltenthermoplastic component. The SAP containing thermoplastic compositionmay be pelletized, pillowed, or cast into molds or drums, etc., forsubsequent remelting and application. Alternatively, all the ingredientsmay be fed simultaneously at the appropriate rates into an extruder. Inthe case of extruders, the compounding and application of the SAPcontaining composition may be achieved in a single process.

In the case of foaming, it is preferred to first coat the SAP particleswith a chemical blowing agent. The coated SAP particle is admixed withthe thermoplastic component at a temperature below the activationtemperature of the chemical blowing agent to prevent prematureunintended foaming. The composition is then formed into a film or coatedonto a substrate at a temperature or condition sufficient to activatethe chemical blowing agent. The chemical blowing agent is surmised tocreate a gaseous cavity or void with the thermoplastic component withthe SAP particle positioned within the void. Preferably, a sufficientamount of coated SAP is employed such that an open cell foam structureis created.

In another embodiment the SAP particles may be coated with thethermoplastic component in particulate form. The coated SAP particle maythen be positioned within an article or on a substrate and then heatactivated to adhere the SAP particle in place.

The coating of solid particles is done in a number of ways. Both spraydrying and prilling are inexpensive methods for coating of particles. Inboth these processes the particle to be coated is added to the melt orsolution and during atomization the coating is done. Another suitablemethod called Magnetically Assisted Impact Coating (MAIC), available byAveka Inc. (Woodbury, Minn.), coats particle onto particle by means of apeening process. By adding a small coating particle onto a largeparticle core into an assembly of small oscillating magnets, the smallparticles are readily coated onto the core particles. A preferred methodis a two step process of coating the SAP particle with a binder and thencontacting the binder coated particle with a powder as described in U.S.Pat. No. 5,688,449 issued Nov. 18, 1997, incorporated herein byreference.

The viscosity of the mixture of thermoplastic component and SAP is lessthan about 200,000 cPs, preferably less than about 100,000, morepreferably less than 50,000 at 350° F. (177° C.), and most preferablyexhibits the same molten viscosity properties as previously describedfor the thermoplastic component alone.

The thermoplastic composition of the present invention gels at a rateequal to or faster than that of the superabsorbent polymer alone.Preferably, the composition gels in less than 3 hours, preferably inless than 2 hours, more preferably in less than 1 hour, even morepreferably in less than 30 minutes, and most preferably in less thanabout 15 minutes. Further, for small particle size SAP, the totalabsorption capacity of the inventive composition is equal to or greaterthan that of the superabsorbent polymer alone.

The composition of the present invention may be applied by any hot meltapplication technique such as slot coating, spiral spraying, screenprinting, foaming, engraved roller or meltblown adhesive applicationtechniques. When applied in this manner, the inventive thermoplasticcomposition may be present as a coating, fiber, nonwoven web, or filmlayer on at least one substrate or as a portion of an article.Preferably, to improve the rate of absorption of the SAP, theapplication conditions are chosen to maximize the surface areas of thecomposition. The composition of the present invention may also be formedinto a film layer. If a continuous film layer is desired, it ispreferred to use a non-contact slot coating application techniquedescribed in U.S. Pat. No. 5,827,252 issued Oct. 27, 1998, incorporatedherein by reference.

The SAP containing thermoplastic composition of the present invention isuseful for a variety of end-uses, particularly those which employsuperabsorbent polymers such as disposable absorbent articles such asdisposable diapers, feminine napkins and medical dressings as well asmoisture barriers for optical cable applications and a variety ofagricultural applications targeted at increasing humectancy. Theinventive composition has further utility in packaging application forfood and drugs for absorbing moisture and fluid, for building materialsfor preventing condensation and waterproofing. Accordingly, thethermoplastic composition may be applied to a variety of substratesusing any suitable method, particularly the hot melt adhesiveapplication techniques described above. Substrates in which SAP iscommonly applied to includes various film materials such as thoseemployed as diaper backsheets and tape backings, absorbents such as woodpulp, paper, tissues and towels, nonwovens, and various cable componentssuch as sheathing and jacketing materials.

The invention is further illustrated by the following non-limitingexamples. All composition exemplified are expressed in wt-% unless notedotherwise.

EXAMPLE

Test Methods

1. Melt Viscosity is determined in accordance with the followingprocedure using a Brookfield Laboratories DVII+Viscometer in disposablealuminum sample chambers. The spindle used is a SC-27 hot-melt spindle,suitable for measuring viscosities in the range of from 10 to 100,000centipoise. The sample is placed in the chamber, which is in turninserted into a Brookfield Thermosel and locked into place. The samplechamber has a notch on the bottom that fits the bottom of the BrookfieldThermosel to ensure that the chamber is not allowed to turn when thespindle is inserted and spinning. The sample is heated to the desiredtemperature, with additional sample being added until the melted sampleis about 1 inch (2.5 cm) below the top of the sample chamber. Theviscometer apparatus is lowered and the spindle submerged into thesample chamber. Lowering is continued until brackets on the viscometeralign on the Thermosel. The viscometer is turned on, and set to a shearrate which leads to a torque reading in the range of 30 to 60 percent.Readings are taken every minute for about 15 minutes, or until thevalues stabilize, which final reading is recorded.

2. Total Absorption is determined by drawing-down a molten film orheat-pressing the SAP comprising thermoplastic composition into a film.The film is then cut into a 1 inch (2.54 cm) square and weighed. Thetotal amount of SAP in the film is calculated on the basis of theconcentration of the SAP within the composition. The sample is thenplaced in a 25 ml cup and 10 mls of water is poured on top of the film.After 3 hours, the unabsorbed water is filtered off and weighed. Thetotal amount of water absorbed is reported as well as the amount ofwater absorbed per gram of SAP (total absorbed/total SAP).

3. Rate of Absorption is determined by drawing-down a molten film orheat-pressing the SAP comprising thermoplastic composition into a film.The film is then cut into a 1 inch (2.54 cm) square and weighed. Thetotal amount of SAP in the film is calculated on the basis of theconcentration of the SAP within the composition. The sample is thenplaced in a 25 ml cup and 10 mls of water is poured on top of the film.A stopwatch is started and the time it takes for gelation to occurreported.

4. Melt Index is reported in accordance with ASTM D-1238, condition 190°C./2.16 kg (also known as “Condition E”).

DESCRIPTION OF INGREDIENTS EMPLOYED IN THE EXAMPLES

Tradename Generic Description, Supplier (Location) Thermoplastic PolymerAffinity EG 8200 5 MI, .870 g/cm³ substantially linear ethylene/1-octeneinterpolymer, Dow (Freeport, TX) Affinity EG 8100 1 MI, .870 g/cm³substantially linear ethylene/1-octene interpolymer, Dow (Freeport, TX)Eastman Copolyester biodegradable copolyester, Eastman 14766 (Kingsport,TN) Eco PLA polylactide resin, Cargill (Minneapolis, MN) EVA 25-400 25%vinyl-acetate, 400 MI EVA EVA 28-400 28% vinyl-acetate, 400 MI EVA EVA28-05 28% vinyl-acetate, 5 MI EVA EVA 28-800 28% vinyl-acetate, 800 MIEVA EVA 28-2500 28% vinyl-acetate, 2500 MI EVA EVA 33-44 33%vinyl-acetate, 44 MI EVA EVA 33-400 33% vinyl-acetate, 400 MI EVAHL-6526 polyamide polymer, (H. B. Fuller Company, St. Paul, MN) HL-6582polyamide polymer, (H. B. Fuller Company, St. Paul, MN) HM-1580polyamide polymer, (H. B. Fuller Company, St. Paul, MN) HL-6594polyamide polymer, (H. B. Fuller Company, St. Paul, MN) HL-6108polyamide polymer, (H. B. Fuller Company, St. Paul, MN) Kraton D-111740% diblock, 17% styrene, 106 MI, styrene- isoprene-styrene blockcopolymer (Shell) Kraton G-1657 35% diblock, 13% styrene, 370¹¹ solutionviscosity styrene-ethylene/butylene-styrene block copolymer (Shell)Plasticizers Benzoflex 50 dipropylene-diethylene glycol dibenzoate,Velsicol (Rosemont, IL) Benzoflex 9-88 dipropylene glycol dibenzoate,Velsicol (Rosemont, IL) Citroflex A4 special citrate ester from citricacid, Morflex Inc. (Greensboro, NC) Epolene C-3 polyethylene wax,Eastman Chemical Co. (Kingsport, TN) Epolene C-16 polyethylene wax,Eastman Chemical Co. (Kingsport, TN) Microwax 180 polyethylene waxParaflint H4 Fischer-Tropsch wax, Moore & Munger (Shelton, CT) Paraffin155 155° melt point paraffin wax Penznap N-500 500 viscosity naphthenicoil Santicizer 160 1,2 benzene dicarboxylic acid, butylphenylmethylester, Solution Inc. (St. Louis, Missouri) Uniplex 214N-butyl benzene sulfonamide, Unitex (Houston, TX) Tackifiers Escorez5400 100° C. hydrogenated dicyclopentadiene resin (Exxon, Houston, TX)Foral AX hydrogenated rosin, Hercules (Wilmington, DE) Nirez V-2040 118°C. terpene phenolic based resin (Arizona, Panama City, FL Zonester 10094° C. rosin based resin (Arizona, Panama City, FL Additives SurfactantJL80-X alcohol ethoxylate surfactant, Huntsman (Houston, TX) Irganox1010 hindered phenol antioxidant, Ciba Geigy (Hawthorne, NY) Irganox1076 hindered phenol antioxidant Ciba Geigy (Hawthorne, NY)Superabsorbent Polymers Aquapearl 1250H sodium polyacrylate, MitsubishiChemical Co. (Tokyo, JP) Cabloc AP-80HS lightly crosslinked sodiumpolyacrylate, Stockhausen (Greensboro, NC) Favor 800 2-propenoic acidpolymers with hydroxyl ethenol homopolymer, Stockhausen (Greensboro, NC)

Due to differences in base chemistry as well as particle size, the geltime of commercially available grades of SAP varies widely. The particlesize distribution and gel time of the SAP employed in the examples canbe characterized as follows in Table I. “D(10%), D(50%), and D(90%)”refers to the percentage of particle below X microns.

Hence, in the case of ASAP 2000, 10% of the particles have a particlesize of less than 12.5 microns, 50% of the particles have a particlesize of less than 62.9 microns, and 90% of the particles have a particlesize of less than 561.7 microns.

TABLE I Tradename of SAP D(10%) D(50%) D(90%) Weight (g) Gel Time Cabloc80HS 12.5 62.9 118 0.30  9 minutes Cabloc 80 HS 0.15 25 minutes ASAP2000 208.8 395.5 561.7 0.31 1 Min. 20 (Standard) Sec Femdry 31 0.31 20Sec

Since particle size distribution SAP tends to be very disperse, Favor800 was separated into fractions with Vortisiv RBF 8 (MM Industries,Salem, Ohio) metallic sieve and separation equipment. The resultingthree portions had particles >425 microns, particles 180-425 microns,and particles <180 microns.

Examples 1-5 of Table II employ a thermoplastic adhesive compositioncomprising 80 g of Uniplex 214, 304 g of EVA 28-800, 36 g of SurfactantJL-80X and 4 g of Irganox 1076 in combination with Favor 800 superabsorbent polymer at the indicated concentration and particle size. Bycomparing Example 1 to Example 4, the effect of increasing SAPconcentration as a function of absorption rate is exemplified. Example 1and 4 both contain the same particle size SAP, >425 microns. However,the composition comprising 40 wt-% SAP gelled 2.5 times faster than thecomposition employing only 30 wt-%. Examples 2 -4 employ 40 wt-% of thesame SAP differing only with respect to the particle size of the SAP.These examples demonstrate that the fastest rate of gelation is achievedwith the smallest particle size. The sample employing <180 micronparticle size SAP absorbed the fluid 4 times faster than the sampleemploying the 180-425 micron SAP.

TABLE II Rate of Absorption Example 1 Adhesive + 30 wt-% > 425 microns1680 seconds Example 2 Adhesive + 40 wt-% 180-425 microns  900 secondsExample 3 Adhesive + 40 wt-% < 180 microns  160 seconds Example 4Adhesive + 40 wt-% > 425 microns  660 seconds Example 5 Adhesive + 40wt-% ASAP 2000 >18000 seconds  Example 6 Adhesive + 40 wt-% AP80HS  840seconds μm = micron

Tables III to XI exemplify compositions of the present inventionemploying a variety of water insensitive thermoplastic polymers. Example10 of Table III and Examples 69 and 70 of Table XI employ asubstantially linear ethylene interpolymer. Examples 9 and 12-14 ofTable III and IV as well as Tables V to IX in their entirety employ anethylene interpolymer comprising a polar comonomer. Examples 7, 8 and 11of Table III and Example 71 of Table XI depict compositions wherein thethermoplastic component is based on a biodegradable thermoplasticmaterial.

Example 7 was found to absorb 10 mls of water in 100 seconds, whereasExample 8 was found to exhibit a slower absorption rate of 190 seconds.Additionally, Example 8 was noted to be very flexible due to theincorporation of the block copolymer.

Table IV exemplifies the rate of absorption for various inventivecompositions of the present invention as well as commercially availablecomparative examples.

According to infrared analysis as well as solvent extraction andcentrifugation analytical techniques, Comparative A is believed tocomprise about 33.8 wt-% of a 33% vinyl acetate/44 MI EVA, about 47.3wt-% high molecular weight (about 10,000) polyethylene glycol, and about18.9 wt-% sodium salt of polyacrylic acid, whereas Comparative B isbelieved to comprise about 42.6 wt-% of a 28% vinyl acetate/400 MI EVA,about 26.8 wt-% polyoxyethylene stearate, about 29.5 wt-% polyacrylicacid, and about 1.1 wt-% wax. Comparative C represents a compositionmade in accordance with Doi et al., U.S. Pat. No. 4,977,211.Specifically, 45 wt-% of LV-780 ethylene-vinyl acetate was combined with15 wt-% of USR E P02P polyethylene and 40 wt-% of Aquapearl 1250H. Therelatively slow absorption rate is surmised to be attributed to the highcohesive strength of the thermoplastic component.

The EVA content of the inventive EVA based compositions of Tables V andVI varies from 20 wt-% to about 70 wt-%. The rate of gelation increasesdramatically at SAP concentrations greater than 30 wt-%. Further, bycomparing Examples 15 to 16 of Table V, it is apparent that the additionof plasticizer tends to further increase the rate of acquisition. TheApplicants surmise that this effect is attributed to the increasedpolarity contributed by the plasticizer and/or a further reduction incohesive strength of the thermoplastic component as a result of thedilution.

A 0.15 g sample of the superabsorbent polymer Cabloc 80HS alone, in theabsence of being combined with a thermoplastic composition in Table I,took 25 minutes to gel. However, Examples 13-15, all containing aboutthe same amount of SAP gel significantly faster, ranging in rate ofgelation from about 3 minutes to about 13 minutes. The Applicantssurmise that the thermoplastic component separates the individual SAPparticles from each other. Accordingly, each SAP particle can absorbfluid and swell independently, essentially unaffected by the surroundingSAP particles. Hence, gel blocking, the phenomena wherein the gelled SAPparticles create a barrier and prevent the migration of fluid to theungelled SAP particles, is reduced, increasing the rate of gelation.

Table VII demonstrates the effect of polar comonomer content and meltindex on the rate of gelation. As exemplified by Examples 27, 28 and 30as the comonomer content increases from 25 wt-% to 28 wt-% to 33 wt-%,the rate of gelation decreases from 24 hours, to about 30 minutes toabout 15 minutes. Hence, polar comonomer contents of greater than 25wt-% are preferred, and greater than 28 wt-% most preferred. Further, asexemplified by Examples 29 and 31-34, as the melt index increases, thegel rate decreases. However, regardless of the melt index of theethylene interpolymers, all these examples exhibit a substantiallyfaster gel rate than Comparative Examples A to C. The Applicants surmisethat the relatively low concentration of SAP causes the reduced gel rateof the comparative examples in view of Examples 21 to 24 of Table IVdepicting the gel rate of high SAP containing formulations in comparisonto low SAP containing formulations.

Table VIII exemplifies compositions of the present invention comprisingwax. In comparison to Example 33, a portion of the plasticizer may bereplaced with wax resulting in similar gel rates. The use of Paraffin155 and Microwax 180 results in faster gel rates. However, as depictedby Example 44, this accelerated rate can only be achieved by employing acombination of polar plasticizer and wax, since wax alone results in aslower gel rate.

Examples 45 to 49 of Table IX exemplify compositions of the presentinvention comprising tackifier. In comparison to Example 33, byreplacing a portion of the plasticizer with tackifier the compositionexhibits comparable gel rates. Examples 50 to 56 of Table IX as well asExamples 9 and 12 of Tables III exemplify compositions of the presentinvention comprising surfactant. Example 37 also contains 4.5 wt-% ofSurfactant JL80-X. As in the case of tackifiers, a portion of the polarplasticizer may be replaced with surfactant resulting in comparable andin some instances accelerated gel rates.

Table X exemplifies compositions comprising water insensitive polyamidesin combination with polar plasticizer as the thermoplastic component.Employing polyamides is advantageous to increase the heat resistance aswell as increase the concentration of SAP. Example 68 employs 70 wt-%SAP, yet remains flexible.

Table XI depicts compositions of the present invention wherein thethermoplastic component contributes elastomeric properties. Examples 69and 70 employ a substantially linear ethylene/alpha-olefin interpolymer,whereas examples 71 and 72 employ saturated block copolymers.Specifically, Preblend A contains 7 wt-% Kraton G-1651, 17 wt-% KratonG-1650, 75.25 wt-% Kaydol mineral oil and 0.25 wt-% Irganox 1010. Thesecompositions can advantageously be sprayed to form a flexible web orslot coated to form a flexible film. The film expands several folds indimension when exposed to water depending on the concentration of SAP.Surprisingly, the film maintains its integrity after swelling.

TABLE III Ingredient Tradename Ex. 7 Ex. 8 Ex. 9 Ex. 10 Ex. 11 Ex. 12Ex. 13 Ex. 14 Cabloc AP-80HS 50 50.0 49.8 50 54.90 50.10 40 Aquapearl1250H Irganox 1076 0.4 0.5* 0.5* Eastman 30 31.5 Copolyester 14766Kraton D-1117 8.0 Santicizer 160 20 10.5 13.63 Benzoflex 50 9.10Benzoflex 9-88 22.72 Citroflex A4 10.15 18 18 EVA 28-400 36.2 EVA 28-80036.28 41.5 41.5 Eco PLA 34.94 Surfactant JL80-X 4.50 Affinity EG 820027.27 Total Parts 100.0 100.0 99.96 99.99 99.99 100 60 100.01 *Irganox1010

TABLE IV Dry Time Viscosity of Thermoplastic Sample Elapsed untilComponent @ 350° F. (177° C.) Example Wt. Gelation CPs Ex. 9 0.3716 2′38″ Ex. 11 0.2808 3′ 30″ 870 Ex. 12 0.2837 4′ 0″  3065 Ex. 10 0.4500 15′0″  Ex. 13 13″ 6740 Ex. 14 12″ 11,900 Comparative A 0.3218 >3 hoursComparative B 0.3300 >3 hours Comparative C 300 minutes

TABLE V SAP Cabloc EVA Santicizer Film Film 80 HS 28-800 160 TOTALThickness Weight* Gel Time Example (wt-%) (wt-%) (wt-%) (%) Mils gramsminutes Ex. 15 50.0 30.0 20.0 100.0 14 0.268 3 Ex. 16 50.0 37.5 12.5100.0 15 0.263 5 Ex. 17 40.0 45.0 15.0 100.0 14 0.264 13 Ex. 18 30.052.5 17.5 100.0 16 0.227 480 Ex. 19 20.0 60.0 20.0 100.0 17 0.242 1440Ex. 20 10.0 67.5 22.5 100.0 18 0.264 >4320 *Since the compositioncomprises 50 wt-% SAP, the weight of SAP = “Film Weight”/2

TABLE VI EVA EVA Benzoflex Santicizer Cabloc Film Film 33-400 33-44 50160 80-HS Thickness Weight Example (wt-%) (wt-%) (wt-%) (wt-%) (wt-%)mils grams Gel Time Ex. 21 11.16 18.84 20.00 50.00  9.0 0.1762 7 min 25sec Ex. 22 17.85 30.15 32.00 20.00 10.6 0.1931 over 6 hours Ex. 23 11.1618.84 20.00 50.00 11.5  0.19999 8 min & 40 sec Ex. 24 17.85 30.15 32.0020.00 11.8 0.1800 over 6 hours

TABLE VII Example # 25 26 27 28 29 30 31 32 33 34 Ingredient Cabloc 80HS 50 50 50 50 50 50 50 50 50 50 EVA 25-400 50 EVA 28-400 50 35 EVA33-400 50 EVA 28-800 36.3 34.5 30 EVA 28-2500 50 30 EVA 28-03 18.2Citroflex A-4 15 31.8 20 15 20 Uniplex 214 13.2 Irganox 1010 0.5 0.5Tests results and observations Film appearance Flexible Flexible StrongStrong Flexible Strong Strong Flexible Good Flexible bleed flexibleflexible flexible flexible flexible film Avg. Gel time 5 min 6 min over24 15 min. Expands 36 min. 6 min 4 min. 6 min 1 min (1″ × 1″ (2.54 cm ×hours 30 sec. while 15 sec. 15 sec 33 sec. 50 sec 40 sec 2.54 cm) about0.3 g gelling film in 10 ml water) (13 min)

TABLE VIII Example No. 35 36 37 38 39 40 41 42 43 44 Cabloc 80 50.0 50.050.0 50.0 50.0 50.0 50.0 50.0 50.0 50.0 HS EVA 28-800 29.7 29.7 29.729.7 29.7 29.7 24.0 24.0 24.0 34.5 AC-400 8.0 Paraffin 8.0 16.0 155FMicrowax 8.0 16.0 15.0 180F Epolene C-3 8.0 16.0 Epolene C-16 8.0Paraflint H4 8.0 Citroflex A-4 12.0 12.0 12.0 12.0 12.0 12.0 9.7 9.7 9.7Irganox 1010 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.5 Property Testsresults and Gel time (fluid absorption) Film less less flexible flexibleflexible slightly slightly slightly slightly slightly appearanceflexible flexible flexible brittle brittle brittle brittle Avg. Gel 5 33 6 6 7 2 2 2 9 time (1″ × 1” minutes minutes minutes minutes minutesminutes minutes minutes minutes minutes (2.54 cm × 15 45 20 20 45 48 3052 45 2.54 cm) seconds seconds Seconds seconds seconds seconds secondsseconds seconds about 0.3 g film in 10 ml water)

TABLE IX Example No. 45 46 47 48 49 50 51 52 53 54 55 56 IngredientCabloc 80 HS 50.0 50.0 50.0 50.0 50.0 48.9 47.0 47.0 47.0 40.0 40.0 40.0EVA 28-800 29.7 29.7 29.7 29.7 24.0 33.6 32.4 32.4 32.4 40.0 40.0 41.5CAB-O-SIL- 2.5 m5 Emerest 2400 6.0 Pluronic F-38 6.0 5.0 Pluronic 6.05.0 F0108 Zonester 100 8.0 16.0 Nirez V-2040 8.0 Escorez 5400 8.0 ForalAX 8.0 Citroflex A-4 12.0 12.0 12.0 12.0 9.7 14.5 14.1 14.1 14.1 15.015.0 18.0 Irganox 1010 0.3 0.3 0.3 0.3 0.3 0.5 0.5 0.5 0.5 0.5 PropertyTests results and Gel time (fluid absorption) Film flexible flexibleflexible sets sets flexible flexible flexible flexible flexible flexibleflexible, appearance slow, slow spray- flexible and able flexible Avg.Gel time 5 6 7 5 5 6 6 6 5 4 4 (1″ × 1″ (2.54 minutes minutes minutesminutes minutes minutes minutes minutes minutes minutes minutes cm ×2.54 cm) 40 30 25 15 20 30 40 35 5 35 50 about 0.3 g seconds secondsseconds seconds seconds seconds seconds seconds seconds seconds secondsfilm in 10 ml water)

TABLE X Example # 57 58 59 60 61 62 63 64 65 66 67 68 Ingredient HL-652642.0 32.0 8.0 6.4 40 24.0 HL-6582x 42.0 32.0 20.0 32.0 25.6 HM 1580 40.020.0 HL 6594 40.0 HL 6108 40.0 Benzoflex 9- 10.0 88 Uniplex 214 8.0 8.08.0 8.0 10.0 10.0 10.0 8.0 10.0 10 6.0 Cabloc 80 50.0 60.0 50.0 60.050.0 50.0 50.0 50.0 60.0 50.0 50 70.0 HS Irganox 1010 Test results andobservations Film slow slow brittle very flexible flexible slow brittlebrittle flexible flexible flexible appearance setting setting brittlesetting slow flexible flexible tacky setting and tacky Avg. Gel 7 min. 5min. 4 min. 4 7 min 4 min. 2 min 2 min. 2 min 2 min. 12 time (1″ × 1″ 5sec. 20 sec. minutes 30 sec. 40 sec. 20 sec. 20 sec. minutes (2.54 cm ×20 2.54 cm) seconds about 0.3 g film in 10 ml water)

TABLE XI Example No. 69 70 71 72 Ingredient Cabloc 80 HS 50 50 50 50Irganox 1010 Benzoflex 8-88 12 15 10 Ciroflex A-4 Penznap N500 oil 26 20Kraton G1657  5 Preblend A 50 40 Copolyester 14766 EG 8100 12 10Property test results Film very elastic, didn't bleed, flexible flexibleflexible, flexible, expanded in elastic, fluid bleed. expandable Geltime over 30 min. 7 minutes Expanded 7 minutes in one hr.

What is claimed is:
 1. A thermoplastic composition comprising athermoplastic component comprising at least one thermoplastic polymerand at least one water insensitive diluent having polar functionality;and at least one superabsorbent polymer.
 2. The thermoplasticcomposition of claim 1 wherein said thermoplastic component is waterinsensitive.
 3. The thermoplastic composition of claim 1 wherein saiddiluent is a plasticizer.
 4. The thermoplastic composition of claim 1wherein said diluent is a wax.
 5. The thermoplastic composition of claim1 wherein the diluent is present in an amount ranging from about 5 wt-%to about 30 wt-%.
 6. The thermoplastic composition of claim 1 whereinthe superabsorbent polymer is present in an amount ranging from about 30wt% to about 60 wt-%.
 7. The thermoplastic composition of claim 1wherein the thermoplastic component comprises at least one polymerselected from the group consisting of block copolymers, amorphouspolyolefins, crystalline polyolefins, interpolymers of ethylene andmixtures thereof.
 8. The thermoplastic composition of claim 1 whereinthe composition gels at a rate substantially equal to or faster thanthat of the superabsorbent polymer alone.
 9. An article comprising afilm layer disposed on a substrate, said film layer comprising thethermoplastic composition of claim
 1. 10. The article of claim 9 whereinsaid superabsorbent polymer has a particle size equal to or greater thanthe thickness of the film layer.
 11. A method of making a filmcomprising the steps of providing a molten mixture of a composition ofclaim 1 and forming a substantially continuous film from said moltenmixture.
 12. A nonwoven web comprising the composition of claim
 1. 13. Adisposable article comprising a body fluid pervious topsheet and a bodyfluid impervious backsheet and the composition of claim 1 disposedbetween said topsheet and backsheet.
 14. A thermoplastic compositioncomprising a thermoplastic component comprising at least oneinterpolymer of ethylene having a melt index greater than about 100 g/10minutes and a comonomer content greater than 30 wt-% and at least onesuperabsorbent polymer.
 15. The thermoplastic composition of claim 14wherein the melt index is greater than 400 g/10 min.
 16. Thethermoplastic composition of claim 14 wherein the melt index is greaterthan about 800 g/10 min.
 17. The thermoplastic composition of claim 14wherein the melt index is greater than about 1000 g/10 min.
 18. Thethermoplastic composition of claim 14 wherein the comonomer content isgreater than about 33 wt-%.
 19. The thermoplastic composition of claim14 wherein the comonomer is selected from the group consisting of vinylacetate, n-butyl acrylate, methacrylate and mixtures thereof.
 20. Athermoplastic composition comprising about 25 wt-% to about 50 wt-% of athermoplastic composition having a Brookfield viscosity of less than30,000 cPs at about 180° C. and about 35 wt-% to about 75 wt-% of asuperabsorbent polymer wherein the thermoplastic component consistsessentially of: a) about 10 wt-% to about 50 wt-% of at least one waterinsoluble polymer; b) 5 wt-% to about 30 wt-% of a water insensitiveplasticizer having polar functionality; and c) 0 wt-% to about 40 wt-%of a tackifier, wax, non-polar plasticizer, or a mixture thereof.
 21. Amethod of applying superasborbent polymer to a substrate comprising thesteps of: a) providing a molten mixture comprising the thermoplasticcomposition of claim 1; and b) applying said mixture to a substrate. 22.The method of claim 21 wherein said substrate is selected from the groupconsisting of, film, paper, nonwoven, tissue, and an absorbent core. 23.A thermoplastic composition comprising at thermoplastic componentcomprising at least one thermoplastic polymer and at least one waterinsensitive diluent having polar functionality and at least onesuperabsorbent polymer, said composition gelling at a rate substantiallyequal to or faster than that of the superabsorbent polymer alone.
 24. Afilm layer disposed on a substrate, said film layer comprising athermoplastic composition comprising at least one thermoplastic polymerand at least one water insensitive diluent having polar functionalityand at least one superabsorbent polymer having a particle size equal toor greater than the thickness of the film.